Oligomerization catalyst and process for the production thereof

ABSTRACT

The invention relates to an oligomerization catalyst comprising nickel oxide and silica-alumina support material and to a process for oligomerization of C3- to C6-olefins using the oligomerization catalyst.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a 35 U.S.C. § 119 patent application which claimsthe benefit of European Application No. 18161757.2 filed Mar. 14, 2018,which is incorporated herein by reference in its entirety.

FIELD

The present invention relates to an oligomerization catalyst containingnickel oxide and a silica-alumina support material and to a process forproducing the oligomerization catalyst. The present invention furtherrelates to a process for oligomerization of C3- to C6-olefins using theoligomerization catalyst.

BACKGROUND

Oligomerization is generally understood as meaning the reaction ofunsaturated hydrocarbons with themselves to form correspondinglylonger-chain hydrocarbons, the so-called oligomers. Thus, for example,an olefin having six carbon atoms (hexene) can be formed byoligomerization of two olefins having three carbon atoms. Theoligomerization of two molecules with one another is also referred to asdimerization.

The resulting oligomers are intermediates which may be used for examplefor the production of aldehydes, carboxylic acids and alcohols. Theoligomerization of olefins is carried out on a large industrial scaleeither in the homogeneous phase using a dissolved catalyst orheterogeneously over a solid catalyst, or else with a biphasic catalystsystem.

Among the heterogeneously catalysed processes, oligomerization overacidic oligomerization catalysts is long-established. Systems employedindustrially include for example zeolites or phosphoric acid on asupport. Isomeric mixtures of branched olefins are obtained here. Fornon-acidic, heterogeneously catalysed oligomerization of olefins withhigh dimer selectivity, nickel compounds on support materials arefrequently employed in industry. Thus WO 95/14647 A1 describes a nickelcatalyst comprising a support material consisting of the componentstitanium oxide and/or zirconium oxide, silicon dioxide and optionallyaluminium oxide for olefin oligomerization. Over these catalysts,mixtures of linear butenes are oligomerized to C₈-olefins with aselectivity of below 75%.

WO 95/14647 A1 describes a process for oligomerization of olefins bymeans of an oligomerization catalyst which as active constituents aftersubtracting the loss on ignition after heat treatment at 900° C.comprises 10% to 70% by weight of nickel oxide, calculated as NiO, 5% to30% by weight of titanium dioxide and/or zirconium oxide, 0% to 20% byweight of aluminium oxide, 20% to 40% by weight of silicon dioxide and0.01% to 1% by weight of an alkali metal oxide.

It is believed that the catalytic activity of nickel-based heterogeneouscatalysts for the oligomerization of olefins, especially olefins having3 to 6 carbon atoms, is based on the interaction between nickel cationsand surface aluminium atoms. However, addition of titanium dioxideand/or zirconium dioxide has the result that the total composition has alower percentage of aluminium/aluminium oxide which can result in thecatalytic activity and/or the conversion being reduced. At the sametime, the addition of titanium dioxide and/or zirconium dioxide may havethe result that relatively large amounts of unwanted oligomerizationproducts are formed, especially highly branched oligomers.

SUMMARY

It is accordingly an object of the present invention to provide animproved oligomerization catalyst which does not have the abovementioneddisadvantages. It is a further object of the invention to provide anoligomerization catalyst which can achieve higher selectivities andhigher conversions in the oligomerization without any negative effect onthe service life of the catalyst and the mechanical properties such asstrength.

The object of the present invention was achieved with theoligomerization catalyst according to claim 1 and the oligomerizationprocess according to claim 8. Preferred embodiments are specified in thesubsidiary claims.

DETAILED DESCRIPTION

The oligomerization catalyst according to the invention comprises nickeloxide, an Al-free and Si-containing binder (Al-free signifies: <0.1% byweight Al in the total composition of the binder), preferably silicondioxide, and an amorphous silica-alumina support material, preferably anamorphous aluminosilicate. The binder is a material which ensures thatthe catalyst produced in accordance with the invention has the necessarymechanical strength. In the context of the present invention“x-ray-amorphous” is to be understood as meaning the property of a solidwhich results from the fact that it has no crystal structure, i.e. nolong-range order. In the context of the present invention, however, itcannot be ruled out that the amorphous silica-alumina support materialhas small crystalline domains. The amorphous silica-alumina supportmaterial is therefore not a crystalline material, for example not azeolitic material.

The oligomerization catalyst has a composition of 15% to 40% by weight,preferably 15% to 30% by weight, of NiO, 5% to 20% by weight of Al₂O₃,55% to 80% by weight of SiO₂ and 0.01% to 1% by weight, preferably 0.05%to 0.5% by weight, of an alkali metal oxide, preferably sodium oxide.The figures are based on a total composition of 100% by weight. Theoligomerization catalyst according to the invention moreover has a ratioof tetrahedral coordinated framework aluminium atoms to octahedralcoordinated framework aluminium atoms in the range from 75:25 to 100:0,preferably in the range from 90:10 to 100:0, particularly preferably of100:0, determined by ²⁷Al MAS NMR. The respective values for theoctahedral and the tetrahedral coordination in the abovementioned ratioare to be understood as percentages based on the total number of thepresent aluminium atoms. In a particularly preferred embodiment of thepresent invention, the oligomerization catalyst is substantially freefrom titanium dioxide and/or zirconium oxide, the oligomerizationcatalyst in particular comprising less than 0.5% by weight, preferablyless than 0.1% by weight, particularly preferably less than 0.01% byweight, of titanium dioxide and/or zirconium oxide in its totalcomposition.

The composition and coordinative properties of the oligomerizationcatalyst relate in particular to the state before employment in theoligomerization, i.e. the form in which the catalyst is charged into thereaction zone. The state of the catalyst, in particular of the surfaceatoms of the catalyst, cannot be conclusively determined during theoligomerization. However, in the present case the catalyst also exhibitsa virtually identical composition and virtually identical coordinativeproperties after deinstallation from the reaction zone.

The ratio of the different coordinations of the aluminium atomsdescribed here relates to all aluminium atoms in the silica-aluminasupport material, that is to say both bulk as well as surface atoms. Thebulk structure of aluminosilicates typically consists of SiO₄tetrahedra, AlO₄ tetrahedra and optionally also AlO₆ octahedra to a verysmall extent. However the outward-facing surface of this structure ismissing the oxygen of an adjoining tetrahedron or octahedron. Thesilicon atom at the surface forms a silanol group relatively easily. Thealuminium atom however formally has only a trivalent coordination with afree orbital. Including the free orbital, this corresponds to atetrahedral coordination. The free orbital may undergo coordinativebonding with molecules or atoms, for example ammonia (ammonium form,structure I of the FIGURE below) or to the oxygen of an adjacent silanolgroup (H form, structure II in the FIGURE below). Due to the interactionbetween aluminium and the adjacent oxygen, the OH bond of the adjacentsilanol group is weakened and the OH group can function as a protondonor. With water from the ambient air the oxygen from the watermolecules bonds coordinatively to the aluminium atom as an electrondonor. Three water molecules may become attached, thus forming anoctahedral coordination (see structure III in the FIGURE below).

The coordinative properties of the aluminium atoms of theoligomerization catalyst have an influence on the oligomerization. Inthe prior art the focus is especially on a predominantly octahedralcoordination of the aluminium atoms, such as is described in U.S. Pat.No. 7,572,946 B2 or U.S. Pat. No. 6,733,657 B2. In the present case, ithas surprisingly been found, however, that by adjusting the ratio oftetrahedrally coordinated and octahedrally coordinated frameworkaluminium atoms to values in the range from 75:25 to 100:0, preferablyin the range from 90:10 to 100:0, particularly preferably of 100:0, itis possible to achieve particularly good catalyst properties, such as ahigher conversion and/or a higher selectivity, when using theoligomerization catalyst according to the invention.

The ratio of tetrahedrally coordinated aluminium atoms to octahedrallycoordinated aluminium atoms can be determined by ²⁷Al MAS NMR, whereinthe tetrahedral coordination of the aluminium atoms is detected at 50 to60 ppm and the octahedral coordination of the aluminium atoms isdetected at 0 ppm and these coordinations may be evaluated byintegration of the peaks. The precise measurement of the NMR spectra wasperformed as follows: This initially comprises sample preparation wherethe samples to be investigated are stored for about 2 hours in anatmosphere saturated with water vapor prior to analysis (desiccator,samples at room temperature 2 to 3 cm above distilled water). As aresult, the signal intensity is increased and it is ensured that allsamples have the same starting point. Following this, 300 to 500 mg ofsample material, according to the density, are placed in a ZrO₂ solidstate spinner (external diameter 4 mm) and compacted with slightpressure.

The actual NMR measurements are carried out on a Bruker 400 Avance IIIHD spectrometer with a special solid state sample head. To eliminateanisotropy, for solid-state samples the samples are inclined at about54° and set into rapid rotation (for ²⁷Al e.g. 12 kHz). A simple 90°pulse is used for signal excitation. Owing to the very rapid relaxationof ²⁷Al nuclei, measurements are taken with a very short delay of about50 ms so that a very rapid pulse sequence is possible. The sweep widthis 400 ppm, wherein the sender is set to 0 ppm (measurement range +200to −200 ppm).

The evaluation of the spectra is carried out as follows: Solid statespectra of quadropole nuclei (²⁷Al is a quadrupole nucleus (nuclear spinI=5/2)) often have baselines that are difficult to correct. Baselinecorrection using a polynomial is in most cases suitable for this purposeonce phase correction has been carried out. The rotation side bandsappearing at equidistant spacings (spacing 12 kHz) are outside theevaluation range and thus do not affect the evaluation. The relevantsignals are integrated taking account of the respective line widths andmay be related to one another to determine the percentage proportions (%Al). The spectra are referenced to a saturated Al(NO₃)₃ solution (δ=0.0ppm). A tetrahedral coordination of the aluminium atoms is detected inthe NMR spectrum range from 50 to 60 ppm. An octahedral coordination ofthe aluminium atoms generates a peak around 0 ppm in the NMR spectrum.

According to the invention the oligomerization catalyst may additionallyhave a specific surface area (calculated according to BET) of 150 to 400m²/g, preferably 190 to 350 m²/g, particularly preferably of 220 to 330m²/g. The specific surface area is measured by nitrogen physisorptionaccording to DIN ISO 9277 (2014-01 version) or calculated therefrom.

In a further preferred embodiment the oligomerization catalyst comprisesmesopores and macropores, i.e. has a bimodal pore size distribution. Themesopores of the oligomerization catalyst according to the inventionhave an average pore diameter of 5 to 15 nm, preferably of 7 to 14 nm,particularly preferably of 9 to 13 nm. By contrast the macropores of theoligomerization catalyst according to the invention preferably have anaverage pore diameter of 1 to 100 μm, particularly preferably of 2 to 50μm. The average pore volume of the oligomerization catalyst according tothe invention, i.e. of both the mesopores and the macropores, may be 0.5to 1.5 cm³/g, preferably 0.7 to 1.3 cm³/g. The average pore diameter andthe average pore volume may be determined by mercury porosimetryaccording to DIN 66133 (1993-06 version).

The oligomerization catalyst according to the invention is preferablypresent as granulate. Furthermore the oligomerization catalyst accordingto the invention may have an average particle diameter (d50) of 0.1 mmto 7 mm, preferably 0.5 to 6 mm, particularly preferably of 1 mm to 5mm. The average particle diameter may be determined by imaging methods,in particular by the methods mentioned in the standards ISO 13322-1(2004 Dec. 1 version) and ISO 13322-2 (2006 Nov. 1 version). A suitableinstrument for analysis of particle diameter is for example the Camsizer2006 instrument (Retsch Technology).

In a further preferred embodiment the oligomerization catalyst has abulk crush strength (BCS) of more than 0.5 MPa, preferably of more than0.6 MPa and particularly preferably of more than 0.8 MPa. The BCS valueis a measure of the mechanical strength of mineral granulates. The bulkcrush strength (BCS) of a solid is to be understood as meaning aparameter defined as a pressure in MPa at which 0.5% by weight of finesfraction (i.e. particles screened off using a screen with a mesh size of0.425 mm) are formed when the solid sample is subjected to pressure viaa piston in a tube. For this purpose 20 ml of the solid are prescreenedwith a screen (mesh size: 0.425 mm), filled into a cylindrical sampletube (internal diameter: 27.6 mm, wall thickness: 5 mm, height: 50 mm)and 5 ml of steel spheres (diameter: 3.9 mm) are placed on the topsurface of the solid. The solid is subsequently subjected to different(increasing) pressures for three minutes. The fines fractions formed bythe subjection to pressure are then removed by screening, in each caseweighed as a sum total and the percentage fraction thereof isdetermined. This process is performed until an amount of 0.5% by weightof fines fraction is reached.

An oligomerization catalyst may also be characterized by means of itsmaximum poured density. In a preferred embodiment the oligomerizationcatalyst according to the invention has a maximum poured density of 0.1to 2 g/cm³, preferably 0.2 to 1.5 g/cm³, particularly preferably of 0.3to 1.0 g/cm³. Determination of poured density may be carried out via ameasuring cylinder. The measuring cylinder is filled with a certainvolume of the solid to be investigated, for example via a suitablemetering apparatus such as the DR100 apparatus (Retsch) and themeasuring cylinder is weighed. The maximum poured density may bedetermined from the weight and the volume. It may be necessary tosubtract the residual moisture from the sample weight.

The oligomerization catalyst according to the invention is produced by aprocess comprising the steps of:

a) mixing the amorphous silica-alumina support material and the Al-freeand Si-containing binder optionally also with at least a portion of anickel source, and granulating the thus-produced mixture;b) treating (impregnating) the granulate produced in step a) with atleast a portion of a nickel source provided that the entirety of thenickel source has not already been mixed with the silica-alumina supportmaterial and the amorphous Al-free and Si-containing binder in step a);andc) calcining the granulate to produce the oligomerization catalyst.

The amorphous silica-alumina support material employed in step a)comprises in the calcined state (without Ni) a ratio of tetrahedralcoordinated framework aluminium atoms to octahedral coordinatedframework aluminium atoms of 50:50 to 74:26, preferably 55:45 to 70:30.The ratio of coordination of tetrahedral coordinated framework aluminiumatoms to octahedral coordinated framework aluminium atoms in thesilica-alumina support material therefore differs from the same ratio inthe final oligomerization catalyst and thus changes during theproduction of the catalyst. The proportion of the tetrahedralcoordination in the stated ratio will increase from the employedsilicon-alumina support material to the final oligomerization catalystwhile the proportion of the octahedral coordination falls.

The amorphous silica-alumina support material is an amorphousaluminosilicate comprising 10% to 20% by weight, preferably 12% to 17%by weight, of Al₂O₃ and 80% to 90% by weight, preferably 83% to 88% byweight, of SiO₂. This relates to the composition without any sorbedcompounds (for example water or ammonia) which are for example reportedunder the term loss on ignition in commercially available products. In apreferred embodiment the amorphous aluminosilicate employed as thesilica-alumina support material may have a particle size (d50) in therange from 10 to 80 μm, preferably 15 to 75 μm. The amorphousaluminosilicate employed as the silica-alumina support material moreoverpreferably has a specific surface area (calculated as BET) of 290 to 380m²/g, particularly preferably of 300 to 360 m²/g, measured by nitrogenphysisorption according to DIN-ISO 9277 (2014-01 version). Theproportion of the silica-alumina support material in the total batch(total composition including any and all employed solvents such aswater) in step a) is 20% to 60% by weight, preferably 25% to 50% byweight, when the entirety of the nickel source is already added in stepa). When the nickel source is partially or completely added only in stepb) a sufficient amount of liquid to allow granulation should be added tothe mixture in step a) by addition of a solvent, preferably water or anammoniacal solution.

The Al-free and Si-containing binder likewise employed in step a)(Al-free signifies: <0.1% by weight of Al in the total composition ofthe binder) is preferably silicon dioxide. The Al-free and Si-containingbinder is moreover preferably present not in solid form but rather inthe form of a colloidal dispersion, particularly preferably a silicasol. In a preferred embodiment the solvent in which the Al-free andSi-containing binder, preferably the silicon dioxide, is present indispersed form is water, the dispersion preferably additionallycontaining ammonia for stabilization. The Al-free and Si-containingbinder, preferably the silicon dioxide, is present in the dispersion inan amount in the range from 7% to 50% by weight, preferably 12% to 42%by weight, particularly preferably 20% to 35% by weight. The averageparticle size of the Al-free and Si-containing binder, preferably of thesilicon dioxide, may be 5 to 20 nm, preferably 6 to 10 nm, particularlyin the dispersion (determinable by light scattering methods). Theviscosity of the dispersion comprising the Al-free and Si-containingbinder, preferably the silicon dioxide, may be in the range from 1 to 50mPas, preferably 5 to 25 mPas. The dispersion comprising the Al-free andSi-containing binder, preferably the silicon dioxide, may furtherpreferably have a pH in the range from 7 to 12, preferably 8 to 10. Thedensity of the dispersion comprising the Al-free and Si-containingbinder, preferably the silicon dioxide, is preferably 1 to 1.3 g/cm³,particularly preferably 1.1 to 1.25 g/cm³. The proportion of the Al-freeand Si-containing binder in the total batch (total composition includingany and all employed solvents such as water) in step a) and optionallyb) is 0.5% to 15% by weight, preferably 1% to 10% by weight.

No separate alkali source is added to the mixture in step a) or b). Thecontent of alkali metal oxide derives from the silica-alumina supportmaterial and/or the Al-free and Si-containing binder which may containsmall amounts of alkali metals, in particular sodium. The alkalicontents of support material and binder are to be chosen such that theydo not fall short of a proportion of 0.01% by weight and do not exceed aproportion of 1% by weight.

The nickel source employed in step a) or b) is a solution of a nickelcompound, a paste of a nickel compound or a solution and a paste,wherein in principle any soluble nickel compound can be employed.Included among these are nickel nitrate (Ni(NO₃)₂), nickel acetate(Ni(ac)₂), nickel acetylacetonate (Ni(acac)₂), nickel sulfate (NiSO₄),nickel citrate or nickel carbonate (NiCO₃). Preference is given tonickel nitrate (Ni(NO₃)₂), nickel sulfate (NiSO₄) or nickel carbonate(NiCO₃). The nickel solution is an aqueous or ammoniacal solution. Anammoniacal solution is an aqueous solution admixed with ammonia. Thenickel paste contains water and the nickel paste according to thepresent invention contains less water than the nickel solution (when thesame amount of nickel compound is assumed). Nickel paste is in principlea moistened solid composed of a nickel compound which is incompletelyhydrated and in which hydroxidic nickel compounds are formally alsoformed; in the case of nickel carbonate for example NiCO₃*Ni(OH)₂ butalso non-stoichiometric nickel carbonate hydroxides. In a preferredembodiment the nickel paste contains between 30% and 50% by weight,preferably 35% to 45% by weight, of nickel based on the total weight ofthe paste. The nickel solution may contain nickel in an amount in therange from 1% to 20% by weight, preferably 5% to 15% by weight, in eachcase based on the total weight of the solution.

In a preferred embodiment the nickel solution employed is an ammoniacalNi(CO₃) solution, known as NiHAC solution (a nickel hexamine carbonatecomplex is formed in the solution ([Ni(NH₃)₆]CO₃)) which has a nickelcontent in the range from 1% to 20% by weight, preferably 5% to 15% byweight. Employable as the nickel paste is a paste composed of nickelcarbonate and water as solvent, wherein the nickel is present ascarbonate/hydroxide (general empirical formula NiCO₃*Ni(OH)₂ butnonstoichiometric nickel carbonate hydroxides may also be formed). Thepaste may have a nickel content in the range from 30% to 50% by weight,preferably 35% to 45% by weight. In a particularly preferred embodimentthe production of the oligomerization catalyst employs in step a) and/orin optional step b) a NiHAC solution.

The total amount of nickel source (paste and/or solution) in the totalbatch (total composition of any and all employed solvents such as water)in step a) and optionally b) of the production process is between 40%and 70% by weight, preferably 45% and 65% by weight.

The process according to the invention has the particular feature thatin step a) no titanium dioxide and no zirconium dioxide are added to themixture but rather the oligomerization catalyst is produced withoutaddition of titanium dioxide and zirconium oxide. Any incidences oftitanium dioxide and/or zirconium dioxide in the total composition ofthe oligomerization catalyst are due to impurities/trace incidences inthe employed components.

In step a) the individual components, i.e. the silica-alumina supportmaterial, the Al-free and Si-containing binder and optionally the nickelsource, are mixed with one another in a mixing vessel using an agitatorand simultaneously or subsequently granulated. This may be effectedusing an intensive mixer for example. Mixing and granulation maytypically be performed at ambient pressure. The temperature at whichmixing and granulation may be carried out is preferably in the rangefrom 10° C. to 60° C. The duration of process step a), i.e. of mixingand granulation, is between 5 minutes and 1 hour, preferably between 10and 30 minutes.

In optional step b) the remaining portion of the nickel source,preferably in the form of a NiHAC solution, is added to the granulateproduced in step a) and mixed with the granulate in order to treat thegranulate with nickel. If at least a portion of the nickel source is tobe added in step b) the possibly moist granulate from step a) may bedried prior to the treatment with the nickel source. The dryingtemperature may be 80° C. to 250° C., preferably 100° C. to 220° C.

The nickel source causes a nickel compound to be deposited on thesurface of the silica-alumina support material. As a result at leastsome of the previously octahedral coordinated aluminium atoms at thesurface are fixed in a tetrahedral coordination and after calcinationcan no longer assume an octahedral coordination. The binder is added asthe substance which joins the different materials and is Al-free here toensure that no additional octahedrally coordinated aluminium atoms areintroduced into the catalyst. Any octahedrally coordinated aluminiumatoms in the bulk of the support material remain untouched thereby as aresult of which even after mixing with the binder a certain amount ofoctahedrally coordinated aluminium atoms may be present in the finishedoligomerization catalyst.

The granulate resulting from step a) and/or step b) may still contain atleast a portion of the employed solvent, in particular water. A moistgranulate may therefore be concerned. Before the possibly still moistgranulate is subjected to the calcination in step c) the moist granulatemay be screened, preferably with a screen having a mesh size of 0.1 to1.5 mm. The screened-off portion of the granulate (undersize) may berecycled back to step a) of the granulation.

After the mixing and granulating in step a), optionally after thetreating (impregnating) of a granulate with at least a portion of anickel source in step b) and optionally after the screening of the moistgranulate the granulate may initially be dried in step c). This may beeffected using known apparatuses such as for example belt dryers or thelike. The drying temperature may be in the range from 80° C. to 250° C.,preferably in the range from 100° C. to 220° C.

Before the optionally dried granulate is subjected to the calcinationthe dried granulate may be fractionated in order to establish aparticular particle size of the granulate. Such a fractionation may beachieved for example through the use of at least one screen having adefined mesh size. In a particularly preferred embodiment two screensare used, wherein the one screen has a mesh size of 0.1 to 1.5 mm andthe other screen has a mesh size of 2.5 to 7 mm. The remaining fractions(oversize and undersize) may be recycled to step a) optionally afterpreceding milling.

The optional drying and possible fractionation of the granulate isfollowed by the calcination of the granulate. This may comprise heatingthe granulate in a suitable furnace, preferably in a nitrogen stream,particularly preferably in a nitrogen countercurrent. Air may be addedto the nitrogen stream during the calcination, wherein the amount of airsupplied may be 100 to 10 000 ppm by volume, preferably 300 to 7000 ppmby volume. The calcination temperature may be 400° C. to 900° C.,preferably 450° C. to 700° C., particularly preferably 500° C. to 600°C. This temperature may be maintained over several hours, preferably 5to 20 hours, particularly preferably 8 to 15 hours, before the granulateis cooled. Air may be introduced into the furnace during cooling but theamount of air introduced should be controlled. The amount of the airoptionally supplied is 100 to 10 000 ppm by volume, preferably 300 to7000 ppm by volume.

The cooled granulate/the finished oligomerization catalyst may possiblythen be fractionated once again to establish a particular particle sizeof the cooled granulate. Such a fractionation may be achieved forexample through the use of at least one screen having a defined meshsize. In a particularly preferred embodiment two screens are used,wherein one screen has a mesh size of 0.1 to 1.5 mm and the other screenhas a mesh size of 2.5 to 7 mm. The remaining fractions (oversize andundersize) may be recycled to step a) optionally after precedingmilling.

After the last process step, of calcination and subsequent fractionationafter cooling, the thus-produced oligomerization catalyst has a finaltotal composition of 15% to 40% by weight, preferably 15% to 30% byweight, of NiO, 10% to 30% by weight of Al₂O₃, 55% to 70% by weight ofSiO₂ and 0.01% to 1% by weight, preferably 0.05% to 0.5% by weight, ofan alkali metal oxide. The figures are based on a total composition of100% by weight.

A reduction in conversion and/or selectivity during oligomerization maybe encountered with increasing employment time of the oligomerizationcatalyst. The catalyst according to the invention may be regeneratedafter use in the oligomerization reaction.

Regeneration of the oligomerization catalyst comprises the steps of:

d) burnoff; ande) restoration of the active surface structure of the oligomerizationcatalyst.

After use in oligomerization reactions the oligomerization catalyst mayexhibit deposits of organic substances that require removal. Removal ofthe organic compounds deposited in the catalyst is preferablyaccomplished in step d) by burnoff (oxidation) to form carbon oxides andwater. The burnoff step d) may be performed continuously ordiscontinuously in a furnace, for example in a rotary kiln or a shaftfurnace. For this purpose the oligomerization catalyst (in the form of agranulate) is supplied to the furnace and preferably maintained at apredetermined furnace temperature of 400° C. to 600° C., particularlypreferably of 500° C. to 600° C. The combustion air used during burnoffis supplied in countercurrent and in addition further air is optionallyblown into the granulate (oligomerization catalyst) via suitable inletsto ensure rapid burnoff.

Step e), i.e. the restoration of the active surface structure of theoligomerization catalyst may in a step e1) comprise an (additional)treatment (impregnation) with nickel. The treatment with nickel may beeffected analogously to the production of the oligomerization catalyst(step b)) but optionally with the difference that a nickel solutionhaving a lower nickel concentration than in the production of theoligomerization catalyst may be used. A nickel paste is typically notemployed in the regeneration. The aim here is to deposit additionalamounts of nickel on the oligomerization catalyst. In principle anysoluble nickel compound such as nickel nitrate (Ni(NO₃)₂), nickelacetate (Ni(ac)₂), nickel acetylacetonate (Ni(acac)₂), nickel sulfate(NiSO₄) or nickel carbonate (NiCO₃) may be used therefor to produce anaqueous or ammoniacal nickel solution.

The use of NiHAC solutions obtainable by dissolving nickel carbonate(NiCO₃) in concentrated ammonia solutions, optionally with addition ofammonium carbonate, has proven particularly advantageous. Such solutionsmay be used for the impregnation with nickel contents of 0.5 to 14% byweight, in particular of 2 to 10% by weight, very particularly of 4 to8% by weight.

For nickel application the oligomerization catalyst burned off in stepd) is for example impregnated with a NiHAC solution having nickelcontents of 0.5 to 14% by weight, in particular of 2% to 10% by weight,very particularly of 4% to 8% by weight until saturation of the pores.The impregnation may be performed with a process familiar to thoseskilled in the art such as for example by spraying until permanentappearance of a liquid film on the surface (incipient wetness). If thesolution takeup is about 0.8 to 1.2 g of solution per g ofoligomerization catalyst a deposition of about 0.5% to 6% by weight ofadditional nickel in the form of a basic carbonate can be achieved.

If the oligomerization catalyst is subjected to a step e1), i.e. treatedwith nickel, the oligomerization catalyst should be dried in a suitabledrying apparatus, for example a belt dryer with an air stream or else aconical dryer, at temperatures between 80° C. and 250° C., preferablybetween 100° C. and 220° C., and at standard pressure or else undervacuum.

Step e) comprises at least the step e2), the calcination that would beperformed after an optional step e1). The calcination of theoligomerization catalyst may be performed continuously ordiscontinuously in a suitable furnace, for example a shaft furnace orrotary kiln. In the case of a continuous calcination in step e2) it isfurthermore preferable when a gas continues to be passed through theoligomerization catalyst (granulate) in countercurrent. The gas employedmay be air, nitrogen or a mixture thereof. The gas stream may be 0.2 to4 m³ of gas per kg of granulate and hour and the inlet temperature ofthe gas may be from 400° C. to 800° C., preferably 450° C. to 700° C. Inaddition to this heat introduced via the gas, energy may be introducedby active heating of the walls of the furnace.

The calcination temperature in the furnace may be 400° C. to 800° C.,preferably 450° C. to 700° C., particularly preferably 500° C. to 600°C. This temperature may be maintained over several hours, preferably 5to 60 hours, particularly preferably 10 to 40 hours, before thegranulate is cooled. Cooling is preferably carried out in a nitrogenstream. Nitrogen may additionally be added to the air and the amount ofair should preferably be controlled. The amount of air preferably addedto the nitrogen may be 100 to 10 000 ppm by volume, preferably 300 to7000 ppm by volume.

The oligomerization catalyst according to the invention/a catalystproduced or regenerated by the process according to the invention may beused in particular for the oligomerization of C3- to C6-olefins,preferably C3- to C5-olefins, particularly preferably C4-olefins, orolefin-containing input mixtures based thereupon. The olefins orolefin-containing input mixtures are employed as a reactant stream.

The present invention also provides a process for oligomerization of C3-to C6-olefins, wherein olefin-containing input mixture which containsthe C3- to C6-olefins is passed over a catalyst in at least one reactionzone, wherein the oligomerization catalyst according to the invention isused to catalyse the oligomerization reaction. According to theinvention, a reaction zone comprises at least one reactor and at leastone distillation column in which the formed oligomers can be separated.The process according to the invention can also be operated with two ormore reaction zones. The oligomerization preferably takes place in theliquid phase.

Olefins employed for the process according to the invention include C3-to C6-olefins, preferably C3- to C5-olefins, particularly preferablyC4-olefins, or olefin-containing input mixtures based thereupon whichmay also contain proportions of analogous alkanes. Suitable olefins areinter alia α-olefins, n-olefins and cycloalkenes. The olefins used asreactants are preferably n-olefins. In a particularly preferredembodiment, the olefin is n-butene. According to the invention the term“olefin-containing input mixtures based thereupon” is to be understoodas encompassing any type of mixtures containing the relevant C3- toC6-olefins to be oligomerized in an amount which makes it possible toperform the oligomerization. Olefin-containing input mixtures preferablycontain virtually no further unsaturated compounds and polyunsaturatedcompounds such as dienes or acetylene derivatives. It is preferable toemploy olefin-containing input mixtures containing less than 5% byweight, in particular less than 2% by weight, of branched olefins basedon the olefin proportion. Olefin-containing input mixtures which containless than 2% by weight of branched olefins, in particular iso-olefins,are further preferably employed.

Propylene (C3) is produced on a large industrial scale by cracking ofnaphtha and is a commodity chemical which is readily available.C₅-olefins are present in light petroleum fractions from refineries orcrackers. Industrial mixtures containing linear C₄-olefins include lightpetroleum fractions from refineries, C₄-fractions from FC crackers orsteam crackers, mixtures from Fischer-Tropsch syntheses, mixtures fromthe dehydrogenation of butanes, and mixtures formed by metathesis orfrom other industrial processes. Mixtures suitable for the processaccording to the invention are obtainable for example from theC₄-fraction of a steam cracker. Butadiene is removed in the first stephere. This is accomplished either by extraction or extractivedistillation of the butadiene or by selective hydrogenation thereof. Inboth cases a virtually butadiene-free C₄-cut is obtained, namelyraffinate 1. In the second step, isobutene is removed from theC₄-stream, for example by production of methyl tert-butyl ether (MTBE)by reaction with methanol. Other options include the reaction of theisobutene from the raffinate I with water to afford tert-butanol or theacid-catalysed oligomerization of isobutene to afford diisobutene. Thenow isobutene-free C₄-cut, raffinate II, contains, as desired, thelinear butenes and possibly butanes. The 1-butene may optionally stillbe removed by distillation. Both fractions, the one comprising but-1-eneor the one comprising but-2-ene, may be used in the process according tothe invention.

In a further preferred embodiment C₄-olefin-containing material streamsare supplied to the process as an olefin-containing input mixture.Suitable olefin-containing input mixtures are inter alia raffinate I(butadiene-free C4-cut from the steam cracker) and raffinate II(butadiene-free and isobutene-free C4-cut from the steam cracker).

A further option for producing a suitable olefin-containing inputmixture is that of subjecting raffinate I, raffinate II or a similarlyconstituted hydrocarbon mixture to hydroisomerization in a reactivecolumn. This may include inter alia a mixture consisting of 2-butenes,small proportions of 1-butene and possibly n-butane and also isobutaneand isobutene.

The oligomerization is generally carried out at a temperature in therange from 50° C. to 200° C., by preference 60° C. to 180° C.,preferably in the range from 60° C. to 130° C., and at a pressure of 10to 70 bar, preferably of 20 to 55 bar. If the oligomerization is to becarried out in the liquid phase the parameters pressure and temperaturemust to this end be chosen such that the reactant stream (the employedolefins or olefin mixtures) is in the liquid phase. The weight-basedspace velocities (reactant mass per unit catalyst mass per unit time;weight hourly space velocity (WHSV)) of the olefin-containing inputmixture are in the range between 1 g of reactant per g of catalyst andper h (=1 h⁻¹) and 190 h⁻¹, preferably between 2 h⁻¹ and 35 h⁻¹,particularly preferably between 3 h⁻¹ and 25 h⁻¹.

In one embodiment, the degree of dimerization (also referred to as“percentage selectivity based on dimerization”) after theoligomerization based on the converted reactant is at least 60%, morepreferably at least 75%, particularly preferably at least 80%.

The linearity of an oligomerization product/of the dimers formed isdescribed by the ISO index and represents a value for the average numberof methyl branches in the dimer. Thus (for butene as the reactant)n-octenes contribute 0, methylheptenes contribute 1 and dimethylhexenescontribute 2 to the ISO index of a C8 fraction. The lower the ISO index,the more linear the construction of the molecules in the respectivefraction. The ISO index is calculated according to the following generalformula:

$\frac{\begin{matrix}\left( {{{singly}\mspace{14mu} {branched}\mspace{14mu} {dimers}\mspace{14mu} \left( {\% \mspace{14mu} {by}\mspace{14mu} {weight}} \right)} +} \right. \\\left. {2 \times {doubly}\mspace{14mu} {branched}\mspace{14mu} {dimers}\mspace{14mu} \left( {\% \mspace{14mu} {by}\mspace{14mu} {weight}} \right)} \right)\end{matrix}}{100}$

Accordingly a dimer mixture having an ISO index of 1.0 has on averageprecisely 1 methyl branch per dimeric molecule.

The ISO index of the product from the oligomerization process accordingto the invention is preferably 0.8 to 1.2, particularly preferably 0.8to 1.15.

The oligomers produced by the process according to the invention areutilized inter alia for producing aldehydes, alcohols and carboxylicacids. Thus for example the dimerisation of linear butenes affords anonanal mixture by hydroformylation. This provides either thecorresponding carboxylic acids by oxidation or a C₉-alcohol mixture byhydrogenation. The C₉-acid mixture may be used for producing lubricantsor siccatives. The C₉-alcohol mixture is a precursor for the productionof plasticizers, particularly dinonyl phthalates, or DINCH.

Even without further elaboration it is assumed that a person skilled inthe art will be able to utilize the description above to the greatestpossible extent. The preferred embodiments and examples are therefore tobe interpreted merely as a descriptive disclosure which is by no meanslimiting in any way whatsoever.

The present invention is more particularly elucidated hereinbelow withreference to examples. Alternative embodiments of the present inventionare obtainable analogously.

Example Catalyst Synthesis (Inventive Catalyst 1):

Placed into the mixing vessel of an intensive mixer are a binder(colloidal solution comprising silicon dioxide, SiO₂ content of about30% by weight), a nickel source (NiHAC solution, nickel content between11% to 12.5% by weight) and amorphous silica-alumina (77.2% by weightSiO₂, 12.2% by weight Al₂O₃, remainder: water, ammonia, traces offurther oxides (loss on ignition), average particle size of 22 μm,specific surface area of 320 m₂/g), ratio of tetrahedrally coordinatedframework aluminium atoms to octahedral coordinated framework aluminiumatoms of 65:35 (calcined without Ni)).

Once all components have been added the mixture is stirred at arelatively low speed to ensure effective distribution. A subsequentincrease in the speed of the stirrer brings about a slow densificationand granulation of the composition. Stirring is stopped as soon asgranulates having a suitable particle diameter (0.1 mm to 7 mm) areobtained. The thus obtained granulate is dried at about 120° C. andsubsequently screened using two screens to remove from the granulateexcessively small or excessively large particles.

The granulate is then calcined in a furnace. For the calcination thegranulate is heated to a temperature between 500° C. to 600° C. and thistemperature is maintained for about 10 to 12 hours. The furnace filledwith granulate has nitrogen flowing through it and a ratio of volumes ofgranulate to volumes of nitrogen per hour (standard volumes) of at least1:1000 is maintained. During the cooling of the granulate to roomtemperature about 6000 ppm by volume of air are metered into thenitrogen stream. The cooled granulate corresponds to the finishedoligomerization catalyst. The thus-produced catalyst has a ratio oftetrahedral coordinated framework aluminium atoms to octahedralcoordinated framework aluminium atoms of about 95:5.

Catalyst Synthesis (Noninventive Catalyst 2):

Placed into the mixing vessel of an intensive mixer are a binder(solution composed of boehmite and a 1% by weight nitric acid solution,aluminium content between 15% to 17% by weight), a nickel source (nickelpaste, moistened nickel carbonate, nickel content between 40% to 42% byweight) and amorphous silica-alumina (77.2% by weight SiO₂, 12.2% byweight Al₂O₃, remainder: water, ammonia, traces of further oxides (losson ignition), average particle size of 22 μm, specific surface area of320 m₂/g, ratio of tetrahedrally coordinated framework aluminium atomsto octahedral coordinated framework aluminium atoms of 65:35 (calcinedwithout Ni)).

The silica-alumina, the binder and the solid nickel source are mixed inthe intensive mixer. During the commixing additional liquid componentscomprising a NiHAC solution (nickel carbonate dissolved in concentratedammoniacal solution, nickel content between 11% and 12.5%) and an alkalimetal compound (sodium carbonate dissolved in distilled water) areslowly added into the mixing vessel via a funnel.

The rest of the production, comprising granulation, drying, screeningand calcination, corresponds to the production for catalyst 1. Thethus-produced catalyst has a ratio of tetrahedral coordinated aluminiumatoms to octahedral coordinated aluminium atoms of approximately 65:35.

Use of the Catalysts in the Oligomerization:

In each case about 12 g of the catalyst were filled into a metal tubehaving an internal diameter of 6 mm. Placed in front of and behind thecatalyst were glass pearls having a diameter of 2 mm which serve as apre-heating/cooling phase. The oligomerization was performed using afeed stream at 30 bar and a loading of 7.5 g/h of butene per gram ofcatalyst, wherein the reaction temperature was varied between 80° C. and100° C. The products were analysed by gas chromatography for theconversion of butenes and the linearity of the octenes. The compositionsof the feed stream for the oligomerization are shown in table 1 whichfollows.

The conversions and selectivities achieved for the feed stream as afunction of temperature for catalyst 1 (inventive) and catalyst 2(noninventive) and the ISO indices resulting therefrom are reported intables 2 and 3.

TABLE 1 Composition of feed stream Feed stream isobutane 8.0% n-butane15.3% trans-2-butene 27.9% 1-butene 32.7% isobutene 0.9% cis-2-butene15.2%

TABLE 2 Conversions and ISO indices in oligomerization using catalyst 1Loading (Feed of C4-olefins in g/h per unit mass of catalyst in g) asWSHV: 7.5 h⁻¹ Conversion ISO Temperature based on C4-olefins indexCatalyst 1 80° C. 36.2% 1.09 (inventive) 90° C. 41.6% 1.12 100° C. 44.9% 1.10

TABLE 3 Conversions and ISO indices in oligomerization using catalyst 2Loading (Feed of C4-olefins in g/h per unit mass of catalyst in g) asWSHV: 7.5 h⁻¹ Conversion ISO Temperature based on C4-olefins indexCatalyst 2 80° C. 32.6% 1.11 (noninventive) 90° C. 38.3% 1.10 100° C. 40.6% 1.08

In contrast to catalyst 2 which has a ratio of tetrahedrally coordinatedaluminium to octahedrally coordinated aluminium of about 65:35, theratio for the catalyst according to the invention is 95:5. It hassurprisingly been found that this makes it possible to achieve adiscernible enhancement in conversion in the case of approximatelyconstant ISO indices.

1. An oligomerization catalyst comprising nickel oxide, an Al-free andSi-containing binder (<0.1% by weight Al) and an amorphoussilica-alumina support material, wherein the catalyst has a compositionof from 15% to 40% by weight of NiO, from 5% to 20% by weight of Al₂O₃,from 55% to 80% by weight of SiO₂ and 0.01% to 1% by weight of an alkalimetal oxide, wherein the oligomerization catalyst has a ratio oftetrahedrally coordinated framework aluminium atoms to octahedralcoordinated framework aluminium atoms of 75:25 to 100:0, determined by²⁷Al MAS NMR.
 2. The oligomerization catalyst according to claim 1,wherein the oligomerization catalyst has a specific BET surface area offrom 150 to 400 m²/g, determined by nitrogen physisorption.
 3. Theoligomerization catalyst according to claim 1, wherein theoligomerization catalyst has mesopores and macropores.
 4. Theoligomerization catalyst according to claim 3, wherein the mesopores ofthe oligomerization catalyst have an average pore diameter of from 5 to15 nm determined by mercury porosimetry.
 5. The oligomerization catalystaccording to claim 3, wherein the macropores of the oligomerizationcatalyst have an average pore diameter of from 1 to 100 μm determined bymercury porosimetry.
 6. The oligomerization catalyst according to claim1, wherein the oligomerization catalyst is in the form of granulate. 7.The oligomerization catalyst according to claim 1, wherein theoligomerization catalyst has an average particle diameter (d50) of from0.1 mm to 7 mm, determined by imaging methods according to ISO 13322-1(2004 Dec. 1 version) and ISO 13322-2 (2006 Nov. 1 version).
 8. Aprocess for oligomerization of C₃- to C₆-olefins, wherein anolefin-containing feed mixture containing the C₃- to C₆-olefins ispassed over a catalyst in a reaction zone, wherein the catalystaccording to claim 1 is used for catalysis of the oligomerizationreaction.
 9. The process for oligomerization according to claim 8,wherein C₃- to C₅-olefins are oligomerized and the olefin-containingfeed mixture contains the C₃- to C₅-olefins.
 10. The process foroligomerization according to claim 8, wherein C₄-olefins areoligomerized and the olefin-containing feed mixture contains theC₄-olefins.
 11. The process for oligomerization according to claim 8,wherein the olefin-containing feed mixture contains less than 2% byweight of branched olefins.
 12. The process for oligomerizationaccording to claim 8, wherein the oligomerization takes place in theliquid phase.
 13. The process for oligomerization according to claim 8,wherein the oligomerization is carried out at a pressure of from 10 to70 bar and a temperature of from 50° C. to 200° C., with the provisothat if the oligomerization is carried out in the liquid phase theparameters pressure and temperature are chosen such that the reactantstream is in the liquid phase.
 14. The process for oligomerizationaccording to claim 8, wherein the weight-based space velocity (WHSV) ofthe olefin-containing feed mixture is in the range between 1 h⁻¹ and 190h⁻¹.
 15. The oligomerization catalyst according to claim 2, wherein theoligomerization catalyst has mesopores and macropores.
 16. Theoligomerization catalyst according to claim 2, wherein theoligomerization catalyst is in the form of granulate.
 17. Theoligomerization catalyst according to claim 2, wherein theoligomerization catalyst has an average particle diameter (d50) of from0.1 mm to 7 mm, determined by imaging methods according to ISO 13322-1(2004 Dec. 1 version) and ISO 13322-2 (2006 Nov. 1 version).
 18. Theprocess for oligomerization of C₃- to C₆-olefins, wherein anolefin-containing feed mixture containing the C₃- to C₆-olefins ispassed over a catalyst in a reaction zone, wherein the catalystaccording to claim 2 is used for catalysis of the oligomerizationreaction.
 19. The process for oligomerization according to claim 9,wherein the olefin-containing feed mixture contains less than 2% byweight of branched olefins.
 20. The process for oligomerizationaccording to claim 9, wherein the oligomerization takes place in theliquid phase.